US20070213552A1 - Process For Preparing Dialkyl Dicarbonates - Google Patents
Process For Preparing Dialkyl Dicarbonates Download PDFInfo
- Publication number
- US20070213552A1 US20070213552A1 US11/596,026 US59602605A US2007213552A1 US 20070213552 A1 US20070213552 A1 US 20070213552A1 US 59602605 A US59602605 A US 59602605A US 2007213552 A1 US2007213552 A1 US 2007213552A1
- Authority
- US
- United States
- Prior art keywords
- process according
- formula
- alkyl
- reaction
- chain
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- ZFTFAPZRGNKQPU-UHFFFAOYSA-N dicarbonic acid Chemical class OC(=O)OC(O)=O ZFTFAPZRGNKQPU-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims abstract description 9
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims abstract description 8
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 150000002148 esters Chemical class 0.000 claims description 9
- 150000003973 alkyl amines Chemical group 0.000 claims description 7
- 239000012074 organic phase Substances 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 4
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 2
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 claims 1
- 238000005191 phase separation Methods 0.000 claims 1
- 125000005270 trialkylamine group Chemical group 0.000 claims 1
- 125000001424 substituent group Chemical group 0.000 abstract description 2
- 125000003282 alkyl amino group Chemical group 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 14
- 239000000203 mixture Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 150000001340 alkali metals Chemical class 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 4
- -1 alkyl chloroformates Chemical class 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- XMJHPCRAQCTCFT-UHFFFAOYSA-N methyl chloroformate Chemical compound COC(Cl)=O XMJHPCRAQCTCFT-UHFFFAOYSA-N 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 150000003512 tertiary amines Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- YKGBNAGNNUEZQC-UHFFFAOYSA-N 6-methyl-n,n-bis(6-methylheptyl)heptan-1-amine Chemical compound CC(C)CCCCCN(CCCCCC(C)C)CCCCCC(C)C YKGBNAGNNUEZQC-UHFFFAOYSA-N 0.000 description 2
- WFDIJRYMOXRFFG-UHFFFAOYSA-N CC(=O)OC(C)=O Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N CC(C)=O Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- GZDFHIJNHHMENY-UHFFFAOYSA-N Dimethyl dicarbonate Chemical compound COC(=O)OC(=O)OC GZDFHIJNHHMENY-UHFFFAOYSA-N 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 235000010300 dimethyl dicarbonate Nutrition 0.000 description 2
- 239000004316 dimethyl dicarbonate Substances 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000005956 quaternization reaction Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000006701 (C1-C7) alkyl group Chemical group 0.000 description 1
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 description 1
- AWQXHKHGNWUDDA-UHFFFAOYSA-N 2-methylpropoxycarbonyl 2-methylpropyl carbonate Chemical compound CC(C)COC(=O)OC(=O)OCC(C)C AWQXHKHGNWUDDA-UHFFFAOYSA-N 0.000 description 1
- YOETUEMZNOLGDB-UHFFFAOYSA-N 2-methylpropyl carbonochloridate Chemical compound CC(C)COC(Cl)=O YOETUEMZNOLGDB-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000002051 biphasic effect Effects 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- SWZDQOUHBYYPJD-UHFFFAOYSA-N tridodecylamine Chemical compound CCCCCCCCCCCCN(CCCCCCCCCCCC)CCCCCCCCCCCC SWZDQOUHBYYPJD-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/14—Preparation of carboxylic acid esters from carboxylic acid halides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/02—Preparation of esters of carbonic or haloformic acids from phosgene or haloformates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
- B01D3/143—Fractional distillation or use of a fractionation or rectification column by two or more of a fractionation, separation or rectification step
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0237—Amines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/96—Esters of carbonic or haloformic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
Definitions
- the catalysts used are preferably tertiary alkylamines of the formula (I) where R 1 , R 2 and R 3 are each independently straight-chain or branched C 8 -C 16 -alkyl or C 6 -cycloalkyl.
- reaction is carried out in the presence of at least one tertiary alkylamine of the formula (I) NR 1 R 2 R 3 where
- the process according to the invention may be carried out either batchwise or continuously.
- the reaction is preferably carried out in a stirred tank. In this case, depending on the size of the batch and the cooling performance present, the reaction is generally complete after 10 minutes to 3 hours.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The novel process for preparing dialkyl dicarbonates by reacting the corresponding alkyl haloformates with alkali metal hydroxides, alkaline earth metal hydroxides and/or carbonates in the presence of water-immiscible organic solvents and in the presence of a catalyst is characterized in that the catalyst used is at least one tertiary alkylamine of the formula (I)
NR1R2R3 (I), where the substituents are each as defined in the description.
NR1R2R3 (I), where the substituents are each as defined in the description.
Description
- The present invention relates to a novel process for preparing dialkyl dicarbonates from the corresponding alkyl chloroformates using specific tertiary alkylamines as catalysts.
- Dialkyl dicarbonates find use, for example, as catalysts for the oxidation of sterically demanding amines, as constituents of electrolyte fluids or as constituents of antimicrobial reagents. Dialkyl dicarbonates are also described in the literature as dialkyl pyrocarbonates.
- DE-B 1 210 853 (1961) discloses the reaction of carbonic halides or carbonyl halides with organic hydroxyl compounds or the alkali metal or alkaline earth metal salts thereof and organic water-immiscible solvents and at least equivalent amounts of alkali metal or alkaline earth metal hydroxides or carbonates in a biphasic system, also using catalytic amounts of tertiary amines or quaternization products thereof, the amines or quaternization products thereof used being those which bear at least one ω-hydroxyalkyl, ω-hydroxyalkyl ether or ω-hydroxyalkyl polyether group bonded to nitrogen.
- DE-A 1 418 849 (1961) also describes tertiary amines as particularly suitable catalysts for the preparation of acid derivatives whose tertiary nitrogen atoms are not sterically hindered, excluding tertiary amines, which bear as substituents on the nitrogen the same ω-hydroxyalkyl, ω-hydroxyalkyl ether or ω-hydroxyalkyl polyether groups. In addition to triethylamine and tri-n-butylamine, amines are therefore used here which bear at least one methyl group on the nitrogen, for example N-methyl-di-n-stearylamine. However, these catalysts have disadvantages including their catalysis not only of the formation but also the decomposition of the product, which leads to a reduction in the yield.
- There is therefore a need for an improved preparation process which affords the target product in high yield.
- It has been found that, surprisingly, dialkyl dicarbonates can be obtained particularly advantageously from alkyl haloformates by reaction with alkali metal or alkaline earth metal hydroxides or carbonates when the catalysts used are specific long-chain tertiary alkylamines.
- These are notable for a high catalytic activity without having a decomposing action on the end product, and can be readily removed from the product, for example by distillation.
- The present invention accordingly provides a process for preparing dialkyl dicarbonates by reacting the corresponding alkyl haloformates with alkali metal hydroxides, alkaline earth metal hydroxides and/or carbonates in the presence of water-immiscible organic solvents and in the presence of a catalyst, characterized in that the catalyst used is at least one tertiary alkylamine of the formula (I)
NR1R2R3 (I)
where - R1, R2 and R3 are each independently straight-chain or branched C6-C25-alkyl or C5-C8-cycloalkyl.
- When the process according to the invention is carried out, the catalysts used are preferably tertiary alkylamines of the formula (I) where R1, R2 and R3 are each independently straight-chain or branched C8-C16-alkyl or C6-cycloalkyl.
- When the process according to the invention is carried out, particularly preferred catalysts are trisoctylamine, trisisooctylamine, trislaurylamine, triscaprylylamine or any mixtures of these amines.
- The process according to the invention preferably serves to prepare dialkyl dicarbonates of the formula (II)
where - R4 is straight-chain or branched C1-C20-alkyl by reacting alkyl haloformates of the formula (III)
where - Hal is halogen, preferably F, Cl, Br, I, in particular chlorine, and
- R4 is straight-chain or branched C1-C20-alkyl,
- characterized in that the reaction is carried out in the presence of at least one tertiary alkylamine of the formula (I)
NR1R2R3
where - R1, R2 and R3 are each independently straight-chain or branched C6-C25-alkyl or C5-C8-cycloalkyl, preferably straight-chain or branched C8-C16-alkyl or C6-Cycloalkyl, as a catalyst.
- In the formulae (II) and (III), R4 is preferably straight-chain or branched C1-C8-alkyl, more preferably a —CH—R5R6 radical where R5 and R6 are each independently H or straight-chain or branched C1-C7-alkyl. In particular, R4 is methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl. Especially preferably, R4 is methyl.
- Useful alkali metal or alkaline earth metal hydroxides or carbonates are, for example, LiOH, NaOH, KOH, LiCO3, Na2CO3, K2CO3. Preference is given to using alkali metal hydroxides such as sodium and potassium hydroxide which are preferably used in the form of aqueous solutions. For example, 1 to 50% by weight aqueous alkali metal hydroxide solutions may be used. Preference is given to 5 to 35% by weight solutions, particular preference to 10 to 25% by weight solutions. The alkali metal or alkaline earth metal hydroxides or carbonates can be used, for example, in amounts of 80 to 120 mol % based on haloformic esters used. This amount is preferably in the range of 90 to 110 mol %, more preferably in the range of 95 to 105 mol %.
- Useful water-immiscible organic solvents are, for example, aliphatic and aromatic hydrocarbons, halogenated hydrocarbons, water-immiscible ethers or esters, and dialkyl carbonates. Preference is given to cyclohexane, toluene, xylene, methylene chloride and diethyl ether, in particular toluene and methylene chloride.
- The water-immiscible organic solvent can be used, for example, in amounts of 20 to 90% by weight, preferably of 30 to 80% by weight, more preferably of 40 to 70% by weight, based on the haloformic ester of the formula (I).
- The catalyst of the formula (I) is used generally, based on haloformic ester, in an amount of 0.001 to 0.5 mol %, preferably of 0.005 to 0.05 mol %.
- The process according to the invention may be carried out in a pressure range of 1 to 10 bar, preferably of 1 to 1.5 bar.
- The reaction temperature may, for example, lie between −10° C. and the boiling point (at standard pressure) of the haloformic ester used. It is preferably in the 0 to 50° C. range.
- It is advantageous to ensure good mixing while carrying out the process according to the invention, for example by using stirrers, baffles or circulation pumps.
- The process according to the invention may be carried out either batchwise or continuously. In batchwise mode, the reaction is preferably carried out in a stirred tank. In this case, depending on the size of the batch and the cooling performance present, the reaction is generally complete after 10 minutes to 3 hours.
- Preference is given to carrying out the process according to the invention continuously using a stirred tank, a stirred tank battery or a tubular reactor. In this case, the average residence time in the reactor is generally between 1 and 60 minutes, preferably between 6 and 45 minutes and more preferably between 10 and 20 minutes.
- After the process according to the invention has been carried out, if appropriate after cooling, the reaction mixture separates into two phases. In addition to the solvent, the organic phase comprises the dialkyl dicarbonate prepared and in some cases small amounts of unconverted haloformic ester and the catalyst. The aqueous phase comprises the inorganic salts formed as well as water.
- The reaction product can be obtained in high purity from the organic phase by multistage distillation. The catalyst may be removed as high boilers and used again as the catalyst in the process according to the invention, if appropriate after a purification (recycling).
- It is a particular and surprising advantage of the process according to the invention that the catalyst virtually does not catalyse the decomposition of the dialkyl dicarbonates after the reaction and can therefore be removed by distillation, as a result of which the isolated yield of end product is higher in comparison to conventional processes.
- 1.17 g of trilaurylamine were initially charged in a mixture of 50 ml of toluene and 25 ml of water, and 43.8 g of methyl chloroformate were added dropwise with stirring at an internal temperature of 5° C. Subsequently, a solution of 35.6 g of 45% sodium hydroxide solution in 96.5 ml of water was added dropwise within 30 minutes and the temperature was kept at 15° C. After the mixture had been stirred for 40 minutes, the phases were separated. 23.1 g of dimethyl dicarbonate (85% of theory) were present in the organic phase.
- A mixture of 290 g of 13.8% by weight aqueous sodium hydroxide solution was added dropwise within 35 minutes to a mixture of 138 g of isobutyl chloroformate, 138 g of toluene and 1.42 g of tri-isooctylamine. In the course of this, the reaction temperature was kept at 30° C. The mixture was stirred for a further 15 minutes and cooled, and the phases were subsequently separated. 98.5 g of diisobutyl dicarbonate (=90% of theory) were present in the organic phase.
- 473 g of 12.1% sodium hydroxide solution were pumped within 45 minutes into a mixture of 1.15 g of triisooctylamine, 180 ml of toluene and 156.9 g of methyl chloroformate, in such a way that it was possible to keep the temperature at approx. 17° C. with cooling. The mixture was stirred for a further 30 minutes and the phases were subsequently separated. 86.7 g of dimethyl dicarbonate (91% of theory) and 5.3 g of methyl chloroformate were present in the organic phase.
Claims (10)
1. Process for preparing dialkyl dicarbonates by reacting the corresponding alkyl haloformates with at least one alkali metal hydroxide, alkaline earth metal hydroxide and/or carbonate in the presence of at least one water-immiscible organic solvent and in the presence of a catalyst, characterized in that the catalyst used is at least one tertiary alkylamine of the formula (I)
NR1R2R3 (I)
where
R1, R2 and R3 are each independently straight-chain or branched C6-C25-alkyl or C5-C8-cycloalkyl.
2. Process according to claim 1 , characterized in that the catalyst used is at least one tertiary alkylamine of the formula (I) according to claim 1 where R1, R2 and R3 are each independently straight-chain or branched C8-C16-alkyl or C6-cycloalkyl.
3. Process according to at least one of claims 1 and 2, characterized in that the catalyst used is at least one amine from the group of trisoctylamine, trisisooctylamine, trislaurylamine, triscaprylylamine.
4. Process according to at least one of claims 1 to 3 , characterized in that dialkyl dicarbonates of the formula (II)
where
R4 is straight-chain or branched C1-C20-alkyl are prepared by reacting alkyl haloformates of the formula (III)
where
Hal is halogen and
R4 is as defined above.
5. Process according to at least one of claims 1 to 4 , characterized in that the alkali metal hydroxides, alkaline earth metal hydroxides and/or carbonates are used in the form of aqueous solutions.
6. Process according to at least one of claims 1 to 5 , characterized in that at least one water-immiscible organic solvent from the group of the aliphatic and aromatic hydrocarbons, the chlorinated hydrocarbons, the dialkyl carbonates or the water-immiscible ethers and esters is used.
7. Process according to at least one of claims 1 to 6 , characterized in that the amount of tertiary trialkylamine of the formula (I) used is 0.001 to 0.5 mol % based on the haloformic esters.
8. Process according to at least one of claims 1 to 7 , characterized in that the reaction is carried out at a temperature between −10° C. and a boiling point (at standard pressure) of the haloformic ester used.
9. Process according to at least one of claims 1 to 8 , characterized in that the reaction is carried out in continuous mode.
10. Process according to at least one of claims 1 to 9 , characterized in that, on completion of the reaction, the reaction mixture is worked up to remove the dialkyl carbonate by phase separation and subsequent multistage distillation of the organic phase.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102004023607A DE102004023607A1 (en) | 2004-05-13 | 2004-05-13 | Process for the preparation of dialkyl dicarbonates |
| DE102004023607.0 | 2004-05-13 | ||
| PCT/EP2005/004724 WO2005110964A1 (en) | 2004-05-13 | 2005-04-30 | Method for producing dialkyl dicarbonates |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| US20070213552A1 true US20070213552A1 (en) | 2007-09-13 |
| US7420076B2 US7420076B2 (en) | 2008-09-02 |
Family
ID=34967240
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US11/596,026 Expired - Lifetime US7420076B2 (en) | 2004-05-13 | 2005-04-30 | Process for preparing dialkyl dicarbonates |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US7420076B2 (en) |
| EP (1) | EP1747185B1 (en) |
| JP (1) | JP4521027B2 (en) |
| KR (1) | KR101151112B1 (en) |
| CN (1) | CN1953957B (en) |
| BR (1) | BRPI0510991B1 (en) |
| CA (1) | CA2562855C (en) |
| DE (1) | DE102004023607A1 (en) |
| MX (1) | MXPA06013026A (en) |
| RU (1) | RU2006139096A (en) |
| WO (1) | WO2005110964A1 (en) |
| ZA (1) | ZA200609327B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102219690B (en) * | 2011-04-29 | 2013-10-02 | 浙江手心医药化学品有限公司 | Preparation method for dimethyl dicarbonate |
| DK3507270T3 (en) | 2016-09-02 | 2021-02-22 | Lanxess Deutschland Gmbh | PROCEDURE FOR THE PREPARATION OF DIALCYL DICARBONATES USING TERTIARY AMINES AS CATALYSTS |
| EP3590917B1 (en) * | 2018-07-05 | 2021-04-21 | LANXESS Deutschland GmbH | Method for the preparation of dialkyldicarbonates by amine oxides |
| CN117736098A (en) * | 2023-12-18 | 2024-03-22 | 重庆市化工研究院有限公司 | Synthetic method and production system of DMDC |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3128297A (en) * | 1961-03-31 | 1964-04-07 | Union Carbide Corp | Process for silicon-halogen bond redistribution |
| US3179714A (en) * | 1960-11-16 | 1965-04-20 | Canadian Ind | Stable coating compositions comprising polyepoxide, carboxyl-containing copolymer, and tertiary amine catalyst |
| US3206519A (en) * | 1963-11-19 | 1965-09-14 | Sun Oil Co | Preparation of alkyl aromatic hydrocarbons |
| US3220975A (en) * | 1959-03-19 | 1965-11-30 | Eastman Kodak Co | Tri-isoamylamine catalyst in a process for preparing a polycarbonate |
| US3240796A (en) * | 1961-04-13 | 1966-03-15 | Bayer Ag | Process for the production of pyrocarbonic acid esters |
| US3326958A (en) * | 1961-05-25 | 1967-06-20 | Bayer Ag | Process for the preparation of carbonic and carboxylic acid derivatives |
| US4929748A (en) * | 1988-12-07 | 1990-05-29 | Akzo America Inc. | Method of preparing dialkyl dicarbonates |
| US5231211A (en) * | 1992-09-18 | 1993-07-27 | Ppg Industries, Inc. | Method for preparing di(organo) esters of pyrocarbonic acid |
| US5523481A (en) * | 1993-12-08 | 1996-06-04 | Bayer Aktiengesellschaft | Process for the preparation of dialkyl dicarbonates |
| US6221534B1 (en) * | 1998-11-25 | 2001-04-24 | Wilson Greatbatch Ltd. | Alkali metal electrochemical cell having an improved cathode activated with a nonaqueous electrolyte having a carbonate additive |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1483560A (en) | 1966-06-16 | 1967-06-02 | Inst Khim An Moldavskoi Ssr | Process for obtaining diethyl pyrocarbonate |
| JPH0629225B2 (en) * | 1986-08-20 | 1994-04-20 | 三菱化成株式会社 | Method for producing zirconium-butyl dicarbonate |
| EP0423008B1 (en) * | 1989-10-09 | 1994-12-28 | Rhone-Poulenc Chimie | Method for the production of disecondary- or ditertiaryalkyldicarbonate |
| JP2970050B2 (en) * | 1991-05-31 | 1999-11-02 | 住友化学工業株式会社 | Method for producing di-t-butyl dicarbonate |
-
2004
- 2004-05-13 DE DE102004023607A patent/DE102004023607A1/en not_active Withdrawn
-
2005
- 2005-04-30 EP EP05741200.9A patent/EP1747185B1/en not_active Expired - Lifetime
- 2005-04-30 RU RU2006139096/04A patent/RU2006139096A/en not_active Application Discontinuation
- 2005-04-30 JP JP2007508873A patent/JP4521027B2/en not_active Expired - Fee Related
- 2005-04-30 WO PCT/EP2005/004724 patent/WO2005110964A1/en not_active Ceased
- 2005-04-30 KR KR1020067023583A patent/KR101151112B1/en not_active Expired - Fee Related
- 2005-04-30 BR BRPI0510991-4A patent/BRPI0510991B1/en not_active IP Right Cessation
- 2005-04-30 US US11/596,026 patent/US7420076B2/en not_active Expired - Lifetime
- 2005-04-30 MX MXPA06013026A patent/MXPA06013026A/en active IP Right Grant
- 2005-04-30 CN CN2005800151922A patent/CN1953957B/en not_active Expired - Fee Related
- 2005-04-30 CA CA2562855A patent/CA2562855C/en not_active Expired - Fee Related
-
2006
- 2006-11-09 ZA ZA2006/09327A patent/ZA200609327B/en unknown
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3220975A (en) * | 1959-03-19 | 1965-11-30 | Eastman Kodak Co | Tri-isoamylamine catalyst in a process for preparing a polycarbonate |
| US3179714A (en) * | 1960-11-16 | 1965-04-20 | Canadian Ind | Stable coating compositions comprising polyepoxide, carboxyl-containing copolymer, and tertiary amine catalyst |
| US3128297A (en) * | 1961-03-31 | 1964-04-07 | Union Carbide Corp | Process for silicon-halogen bond redistribution |
| US3240796A (en) * | 1961-04-13 | 1966-03-15 | Bayer Ag | Process for the production of pyrocarbonic acid esters |
| US3326958A (en) * | 1961-05-25 | 1967-06-20 | Bayer Ag | Process for the preparation of carbonic and carboxylic acid derivatives |
| US3206519A (en) * | 1963-11-19 | 1965-09-14 | Sun Oil Co | Preparation of alkyl aromatic hydrocarbons |
| US4929748A (en) * | 1988-12-07 | 1990-05-29 | Akzo America Inc. | Method of preparing dialkyl dicarbonates |
| US5231211A (en) * | 1992-09-18 | 1993-07-27 | Ppg Industries, Inc. | Method for preparing di(organo) esters of pyrocarbonic acid |
| US5523481A (en) * | 1993-12-08 | 1996-06-04 | Bayer Aktiengesellschaft | Process for the preparation of dialkyl dicarbonates |
| US6221534B1 (en) * | 1998-11-25 | 2001-04-24 | Wilson Greatbatch Ltd. | Alkali metal electrochemical cell having an improved cathode activated with a nonaqueous electrolyte having a carbonate additive |
Also Published As
| Publication number | Publication date |
|---|---|
| MXPA06013026A (en) | 2006-12-20 |
| JP2007533703A (en) | 2007-11-22 |
| WO2005110964A1 (en) | 2005-11-24 |
| US7420076B2 (en) | 2008-09-02 |
| DE102004023607A1 (en) | 2005-12-01 |
| EP1747185B1 (en) | 2015-03-04 |
| CA2562855A1 (en) | 2005-11-24 |
| CN1953957B (en) | 2010-06-02 |
| BRPI0510991B1 (en) | 2014-09-23 |
| ZA200609327B (en) | 2008-04-30 |
| EP1747185A1 (en) | 2007-01-31 |
| BRPI0510991A (en) | 2007-12-04 |
| JP4521027B2 (en) | 2010-08-11 |
| HK1097252A1 (en) | 2007-06-22 |
| RU2006139096A (en) | 2008-06-20 |
| CN1953957A (en) | 2007-04-25 |
| KR20070009694A (en) | 2007-01-18 |
| CA2562855C (en) | 2010-08-03 |
| KR101151112B1 (en) | 2012-06-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5523481A (en) | Process for the preparation of dialkyl dicarbonates | |
| US7420076B2 (en) | Process for preparing dialkyl dicarbonates | |
| US6864372B2 (en) | Process for the production of sulfonic esters | |
| EP0372635B1 (en) | Method of preparing dialkyl and diallyl dicarbonates | |
| US10800728B2 (en) | Method for producing dialkyldicarbonates using tertiary amines as catalysts | |
| US10870617B2 (en) | Method for preparing dialkyl dicarbonates using amine oxides | |
| JPH06192260A (en) | Obtention of 3,7-dialkylxanthin from 3-alkylxanthin | |
| US20050203287A1 (en) | Process for the preparation of sulfamate derivatives | |
| US8017798B2 (en) | Method for producing tetrafluoroterephthalic acid difluoride | |
| US11976082B2 (en) | Continuous process for manufacturing alkyl 7-amino-5-methyl-[1,2,5]oxadiazolo[3,4-b]pyridine-carboxylate | |
| US12275690B2 (en) | Method for producing isocyanate compound | |
| US6548678B1 (en) | Method for producing 5-phenoxycarbonylbenzotriazole | |
| JP2001048839A (en) | Production of carbamates |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AS | Assignment |
Owner name: LANXESS DEUTSCHLAND GMBH, GERMANY Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:PRINZ, THOMAS;ECKERT, MARKUS;BUSCHHAUS, HANS-ULRICH;AND OTHERS;REEL/FRAME:018565/0401;SIGNING DATES FROM 20060911 TO 20060925 |
|
| STCF | Information on status: patent grant |
Free format text: PATENTED CASE |
|
| FPAY | Fee payment |
Year of fee payment: 4 |
|
| FPAY | Fee payment |
Year of fee payment: 8 |
|
| MAFP | Maintenance fee payment |
Free format text: PAYMENT OF MAINTENANCE FEE, 12TH YEAR, LARGE ENTITY (ORIGINAL EVENT CODE: M1553); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY Year of fee payment: 12 |